The present invention relates to a very advantageous process for the industrial production of relatively high molecular weight alkenes, in particular of monosubstituted alkenes, by partial hydrogenation of the corresponding alkynes in the liquid phase over fixed-bed supported palladium catalysts with the addition of carbon monoxide (CO) to the hydrogenation hydrogen.
The hydrogenation of alkynes to alkenes is of major industrial importance and is therefore the subject of extensive prior art.
Thus, GB A 871 804 describes an improved partial hydrogenation of acetylene compounds by the suspension procedure using a palladium catalyst (Pd catalyst) which was doped with salt solutions of the metals Zn, Cd, Hg, Ga, In or Tl.
Furthermore, DE A 24 31 929 describes a process for the preparation of 2-butene-1,4-diol by hydrogenation of butynediol in aqueous solution over a catalyst which contains Pd and one of the elements Zn or Cd and at least one of the elements Bi or Te. The catalyst support used is pumice or alumina.
For the partial hydrogenation of the triple bond in intermediates for vitamins and fragrances, lead-doped Pd catalysts, i.e. Lindlar catalysts, are usually used (cf. for example U.S. Pat. No. 2,681,938).
Frequently, these Lindlar catalysts are also deactivated by means of sulfur compounds in order to increase the selectivity (cf. JP A 120 657/81).
U.S. Pat. No. 2,809,215 describes the batchwise hydrogenation of 3,7,11-trimethyl-6-dodecen-1-yn-3-ol over these Lindlar catalysts.
Finally, DE A 26 19 660 discloses a process for the preparation of butenediol, in which butynediol in an inert solvent is hydrogenated in the presence of a catalyst which contains metallic Pd treated with carbon monoxide. This process can additionally be carried out in the presence of from about 200 to 2000 ppm of CO in the hydrogenation hydrogen.
Furthermore, the use of a Pd/BaSO4 catalyst for the preparation of butenediol is disclosed from DE A 26 05 241.
An overview of the industrially used catalyst systems for the partial hydrogenation of triple bonds to give olefinic double bonds is known from M. Freifelder, xe2x80x9cPractical Catalytic Hydrogenationxe2x80x9d, Wiley Interscience, New York, 1971, pages 84 to 126.
All stated processes have the disadvantage that a suspended catalyst having a high Pd content is used. After the hydrogenation is complete, the catalyst must be separated off from the reaction product by settling and filtration.
It has been found that, on the industrial scale, complete removal of the catalyst powder is possible only at very great expense. However, traces of catalyst residues in the end product give rise to difficulties during the further processing or during the other use of the alkenes. There has therefore been no lack of attempts to develop a fixed-bed catalyst having high abrasion resistance to the partial hydrogenation of the triple bond in alkynes in the liquid phase.
EP 0 841 314 describes a process for the hydrogenation of 3,7,11,15-tetramethyl-1-hexadecyn-3-ol (dehydroisophytol), which is carried out over amorphous metal alloys, such as Pd81Si19, in supercritical carbon dioxide, which have been doped with Pb in order to increase the selectivity in the hydrogenation to isophytol. In addition, a sulfur compound, such as 1,2-bis(2-hydroxyethylthio)ethane, had to be added to the hydrogenation mixture in this process, in order to achieve a good yield. The expensive catalyst preparation, the removal and recycling of the carbon dioxide and the additional use of a sulfur-containing compound made the process appear very expensive.
EP 0 412 415 discloses a fixed-bed catalyst for the hydrogenation of 3,7-dimethyloct-1-yn-3-ol (hydrodehydrolinalool) to 3,7-dimethyloct-1-en-3-ol (hydrolinalool), which catalyst contains palladium as an active component and metals such as Sn, Pb, Zn, Cd, Sb or Bi as an inhibitor. The monolithic fixed-bed palladium catalysts described in this patent and doped with inhibitor make it possible to replace the disadvantageous suspension procedure by the technically substantially more advantageous trickle-bed or liquid-phase procedure over the fixed-bed catalyst. The very high abrasion resistance of these catalyst monoliths permits a very high gas and liquid loading.
Unfortunately, it has been found that, when a process described in this patent is carried out continuously over bismuth-doped fixed-bed palladium catalysts over relatively long periods, the selectivity of the hydrogenation of hydrodehydrolinalool to hydrolinalool slowly decreases, i.e. the reaction product contains increasing amounts of the completely hydrogenated 3,7-dimethyloctan-3-ol, which is due to the fact that the bismuth dopant is lost.
EP 754 664 A states that the process according to EP B1 412 415 can be improved by metering small amounts of CO into the hydrogenation gas. The disadvantage of this process is that the space-time yields are still not optimum and that, in the continuous procedure on an industrial scale, the catalysts are not stable and not sufficiently selective over a sufficiently long time.
In the processes according to EP 754 664, EP 0 841 314 and EP 412 415, attention is not paid to the fact that, in the hydrogenation of alkynes, high boilers which adversely affect the overall selectivity always form as a result of oligomerization. However, this formation of high boilers is known from the literature (cf. G. Ertl et al. in xe2x80x9cHandbook of Heterogeneous Catalysisxe2x80x9d, VCH, 1997, page 2172) and is also described in EP 0 827 944.
EP 827 944 describes a process for the hydrogenation of polyunsaturated C2-C8-hydrocarbons over the fixed-bed catalysts disclosed in EP 412 415, the dopants being selected from a relatively large group of metals and the catalyst preparation being extended to include the possibility of impregnating the support materials. However, their use is restricted to C2-C8-hydrocarbons. However, G. Ertl et al. in xe2x80x9cHandbook of Heterogeneous Catalysisxe2x80x9d, VCH, 1997, pages 2202-2204, discloses that the selectivity in the partial hydrogenation of alkynes depends to a great extent on the alkyne to be hydrogenated, since factors such as mass transfer and heat transfer, adsorption and surface reactions on the catalyst greatly affect the selectivity. It is precisely the factors of mass transfer and heat transfer that depend on the viscosity of the reaction medium (cf. for example M. Baerns, H. Hofmann, A. Renken in xe2x80x9cChemische Reaktionstechnikxe2x80x9d, Georg Thieme Verlag Stuttgart, 2nd edition, 1992, pages 67-97), which is generally high for molecules of relatively high molecular weight.
It is an object of the present invention to provide a process for the preparation of alkenes having relatively high molecular weights, i.e. alkenes of about 10 to 30 carbon atoms, preferably monosubstituted alkenes of 10 to 30 carbon atoms, by partial hydrogenation of the corresponding alkynes, which does not have the disadvantages of the suspension procedure, is technically simple to implement and operates with catalysts which are simple to prepare, have long-term stability, have a high overall selectivity and produces very little overhydrogenated products and high boilers.
We have found, surprisingly, that this object is achieved and that monolithic fixed-bed supported palladium catalysts which were obtained by impregnating the heated support material with a palladium salt solution and have been described in EP 0 827 944 for the partial hydrogenation of low molecular weight alkynes can be used with good selectivities for C10- to C30-alkynes, too, if amounts of CO which are in the range from 10 to 2000 ppm are added to the hydrogenation hydrogen or the alkyne to be hydrogenated is mixed with the compound which decomposes to a small extent with CO elimination but otherwise does not further intervene in the hydrogenation.
The present invention accordingly relates to a process for the preparation of alkenes by partial hydrogenation of alkynes in the liquid phase at from 20 to 250xc2x0 C. and hydrogen partial pressures of from 0.3 to 200 bar over fixed-bed supported palladium catalysts which are obtainable by heating the support material in the air, cooling, applying a palladium compound and, if required, additionally other metal ions for doping purposes, molding and processing to give monolithic catalyst elements, wherein
A) alkynes of 10 to 30 carbon atoms are used as starting compounds,
B) the palladium compound and, if required, the other metal ions are applied to the support material by impregnation of the heated and cooled support material with a solution containing palladium salts and, if required, other metal ions and subsequent drying, and
C) from 10 to 2000 ppm of carbon monoxide (CO) are added to the hydrogenation gas or a corresponding amount of CO is allowed to form in the liquid phase by slight decomposition of a compound which is added to the reaction mixture and eliminates CO under the reaction conditions.
The process is particularly suitable for the partial hydrogenation of monosubstituted alkynes, such as 3,7-dimethyloct-6-en-1-yn-3-ol (dehydrolinalool) or 3,7-dimethyloct-1-en-3-ol (hydrodehydrolinalool). The partial hydrogenation of monosubstituted alkynes is known to be substantially more problematic than that of disubstituted alkynes, such as butyne-1,4-diol, since the monosubstituted alkynes can react further during the hydrogenation. Accordingly, the partial hydrogenation of disubstituted alkynes, such as butyne-1,4-diol, is also possible using the novel process.
Examples of suitable starting materials for the novel process are:
Monosubstituted alkynes, such as dehydrolinalool, hydrodehydrolinalool, 1-ethynyl-2, 6, 6-trimethylcyclohexanol and 17-ethynylandrost-5-ene-3xcex2, 17xcex2-diol, 3,7,11,15-tetramethyl-1-hexadecyn-3-ol (dehydroisophytol), 3,7,11-trimethyldodec-1-yn-3-ol, 3,7,11-trimethyl-4-dodecen-1-yn-3-ol and 3,7,11-trimethyl-6-dodecen-1-yn-3-ol (dehydrodihydronerolidol) and disubstituted alkynes, such as 4-methyl-4-hydroxy-2-decyne, 1,1-diethoxy-2-octyne and bis (tetrahydro-2-pyranyloxy)-2-butyne.
The starting compounds can also be used in the form of a mixture of two or more different alkynes. The individual alkenes can then be separated in a manner known per se, for example by distillation, from the resulting mixture of various alkenes.
If the starting alkynes were prepared by reacting acetylene with a ketone, the unreacted ketone may be present as a mixture with the alkynes in the novel process. This even has the advantage that the ketone is capable of eliminating small amounts of CO, which can make the metering in of CO superfluous.
Woven fabrics of inorganic materials, such as Al2O3 and/or SiO2, or woven fabrics of wires comprising plastics, such as polyamides, polyesters, polypropylene, polytetrafluoroethylene, etc., may be used as catalyst support material. However, foil-like or fabric-like metal supports, i.e. foils or woven wire fabrics comprising metals, such as iron, spring steel, copper, brass, aluminum, nickel silver, nickel, chromium steel or chromium nickel steels, are particularly suitable. Foils or woven fabrics of materials having material numbers 1.4767, 1.4401 and 1.4301 have proven particularly useful. The designation of these materials with the stated material numbers is in line with the material numbers stated in the Stahleisenliste, published by the Verein Deutscher Eisenhuttenleute; 8th edition, pages 87, 89 and 106, Verlag Stahleisen mbH, Dusseldorf 1990. The material having material number 1.4767 is also known under the name Kanthal. These metallic supports are pretreated by oxidative heating, preferably in the air, at from 600 to 1100xc2x0 C., preferably from 700 to 1000xc2x0 C.
The application of the palladium is carried out by simple impregnation of the support material with Pd-containing solutions which are prepared by dissolving salts of palladium with inorganic or organic acids, preferably nitrates, in a solvent, preferably water. The metal salt solution may furthermore contain one or more promoter elements, which may originate from groups II to V and IB to VIIIB of the Periodic Table of the Elements. Particularly preferably used dopant metals are Cu, Ag and Au. The impregnation is followed by a drying step in which the woven fabric is preferably moved. This is followed by a calcination step.
The amounts of applied Pd may be from 5 to 1000, preferably from 30 to 500, mg/m2 of fabric area. The amounts of the additional promoters are in general from about 0.5 to 800, preferably from 1 to 500, mg/m2 of fabric area.
The support material coated in this manner with palladium can then be formed by heating at from 200 to 800xc2x0 C., preferably from 300 to 700xc2x0 C., for from 0.5 to 2 hours. Depending on the type of palladium coating, this heating step after the coating can however also be omitted. The catalyst foils, catalyst nets or woven fabric coated in this manner with Pd and, if required, subsequently heated are then expediently molded in a manner known per se to give monoliths or moldings, e.g. Sulzer packings, for installation in the hydrogenation reactor. This makes it possible to establish the desired good flow conditions in the reactor.
After the reduction of the catalyst with hydrogen at from 20 to 250xc2x0 C., preferably from 70 to 200xc2x0 C., which is advantageously carried out in the reactor, the catalyst is ready for use for the novel partial hydrogenation.
The novel process is advantageous if the partial hydrogenation is carried out continuously in a tube reactor by the trickle-bed or liquid phase procedure with product recycling with cross-sectional loading of from 20 to 500, preferably from 100 to 300, m3/m2*h.
It is also very advantageous if, like the liquid product, the hydrogenation gas mixture comprising hydrogen and CO is also circulated with similar cross-sectional loadings.
The rate of hydrogen absorption is a measure of selectivity. If too much hydrogen is reacted per unit time, a high proportion of overhydrogenated byproduct is obtained; if too little hydrogen is reacted per unit time, a high proportion of oligomeric, high-boiling byproducts is obtained. Since the rate of hydrogen absorption is dependent on the CO concentration in the hydrogenation mixture, the novel process opens up the very advantageous possibility of establishing the selectivity by means of the CO metering.
The partial hydrogenation is particularly advantageous on an industrial scale if it is carried out by the liquid phase procedure and the cycle gas is sprayed in very fine distribution into the reactor by means of the liquid stream and a suitable apparatus, such as a liquid-gas compressor. In conjunction with the shaping of the catalyst monoliths and the described gassing of the reactor, high space-time yields are achieved by optimum cross-mixing and good hydrodynamics of the catalyst interface. The partial hydrogenations are carried out at from 20 to 250xc2x0 C., preferably from 60 to 200xc2x0 C., depending on the substance.
The partial hydrogenation is advantageously carried out continuously in one or more reactors connected in series. The hydrogen partial pressure is in general from 0.3 to 200, preferably from 0.5 to 20, bar. The hydrogenations can be carried out with or without exit gas.
With the aid of the novel process, it is possible to prepare many alkenes required as fragrances or intermediates for active ingredients, such as vitamins, in particular monosubstituted alkenes, such as linalool, hydrolinalool, 3,7,11,15-tetramethyl-1-hexadecen-3-ol (isophytol), 3,7,11-trimethyl-1-dodecen-3-ol (tetrahydronerolidol), 3,7,11-trimethyl-1,4-dodecadien-3-ol or 3,7,11-trimethyl-1,6-dodecadien-3-ol (dihydronerolidol), from the corresponding alkynes in good yields and good space-time yields and with constantly good selectivities, also on an industrial scale, in a continuous process over catalysts which can be relatively easily prepared, contain only a small amount of Pd, are abrasion-resistant and are stable over long periods.